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Biocatalytic Enantioselective Oxidation of Sec-Allylic Alcohols with Flavin-Dependent Oxidases

Gandomkar, S., Jost, E., Loidolt, D., Swoboda, A., Pickl, M., Elaily, W., Daniel, B., Fraaije, M. W., Macheroux, P. & Kroutil, W., 19-Nov-2019, In : Advanced Synthesis & Catalysis. 361, 22, p. 5264-5271 8 p.

Research output: Contribution to journalArticleAcademicpeer-review

  • Somayyeh Gandomkar
  • Etta Jost
  • Doris Loidolt
  • Alexander Swoboda
  • Mathias Pickl
  • Wael Elaily
  • Bastian Daniel
  • Marco W. Fraaije
  • Peter Macheroux
  • Wolfgang Kroutil

The oxidation of allylic alcohols is challenging to perform in a chemo- as well as stereo-selective fashion at the expense of molecular oxygen using conventional chemical protocols. Here, we report the identification of a library of flavin-dependent oxidases including variants of the berberine bridge enzyme (BBE) analogue from Arabidopsis thaliana (AtBBE15) and the 5-(hydroxymethyl)furfural oxidase (HMFO) and its variants (V465T, V465S, V465T/W466H and V367R/W466F) for the enantioselective oxidation of sec-allylic alcohols. While primary and benzylic alcohols as well as certain sugars are well known to be transformed by flavin-dependent oxidases, sec-allylic alcohols have not been studied yet except in a single report. The model substrates investigated were oxidized enantioselectively in a kinetic resolution with an E-value of up to >200. For instance HMFO V465S/T oxidized the (S)-enantiomer of (E)-oct-3-en-2-ol (1a) and (E)-4-phenylbut-3-en-2-ol with E>200 giving the remaining (R)-alcohol with ee>99% at 50% conversion. The enantioselectivity could be decreased if required by medium engineering by the addition of cosolvents (e.g. dimethyl sulfoxide).image

Original languageEnglish
Pages (from-to)5264-5271
Number of pages8
JournalAdvanced Synthesis & Catalysis
Volume361
Issue number22
Publication statusPublished - 19-Nov-2019

    Keywords

  • Biocatalysis, Biotransformation, sec-Allylic alcohol, Asymmetric catalysis, Aerobic Oxidation, 1,2-REDUCTION, COMPLEXES, ENONES, FAMILY

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